JPH10204157A - Method for producing polyhydroxycarboxylic acid resin - Google Patents
Method for producing polyhydroxycarboxylic acid resinInfo
- Publication number
- JPH10204157A JPH10204157A JP1150097A JP1150097A JPH10204157A JP H10204157 A JPH10204157 A JP H10204157A JP 1150097 A JP1150097 A JP 1150097A JP 1150097 A JP1150097 A JP 1150097A JP H10204157 A JPH10204157 A JP H10204157A
- Authority
- JP
- Japan
- Prior art keywords
- mixture
- acid resin
- producing
- acid
- hydroxycarboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 23
- 239000011347 resin Substances 0.000 title claims abstract description 23
- 239000002253 acid Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 19
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 10
- 239000004310 lactic acid Substances 0.000 claims abstract description 7
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 7
- 229920002261 Corn starch Polymers 0.000 claims abstract description 6
- 239000008120 corn starch Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 3
- 229920002472 Starch Polymers 0.000 claims description 7
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 claims description 4
- 229920001542 oligosaccharide Polymers 0.000 claims description 4
- 150000002482 oligosaccharides Chemical class 0.000 claims description 4
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical group C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 3
- XMGQYMWWDOXHJM-JTQLQIEISA-N D-limonene Natural products CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 claims description 3
- -1 corn starch Chemical class 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- RFSUNEUAIZKAJO-VRPWFDPXSA-N D-Fructose Natural products OC[C@H]1OC(O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-VRPWFDPXSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 150000002772 monosaccharides Chemical class 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims 4
- 125000000545 (4R)-limonene group Chemical group 0.000 claims 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 244000005700 microbiome Species 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 239000002689 soil Substances 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000008107 starch Substances 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 229920006167 biodegradable resin Polymers 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- MWFOVBOCPFXQMF-UHFFFAOYSA-L dibutyl-chloro-[dibutyl(chloro)stannyl]oxystannane Chemical compound CCCC[Sn](Cl)(CCCC)O[Sn](Cl)(CCCC)CCCC MWFOVBOCPFXQMF-UHFFFAOYSA-L 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
(57)【要約】
【課題】農業・園芸用資材、漁業用資材、粘結剤などに
利用でき、使用後に廃棄されても加水分解及び／又は土
中の微生物などにより二酸化炭素と水に分解されるポリ
ヒドロキシカルボン酸樹脂を容易に製造する方法を提供
すること。
【解決手段】ヒドロキシカルボン酸二量体（たとえばＬ
−ラクチド）またはヒドロキシカルボン酸オリゴマー
（たとえば乳酸オリゴマー）とＤ−グルコース、コーン
スターチなどの糖類との混合物中に重合触媒（好ましく
は１，３−置換−１，１，３，３−テトラオルガノジス
タノキサン）を添加し、減圧下に加熱攪拌するかまたは
有機溶媒中で脱水重合を行うことによりポリヒドロキシ
カルボン酸樹脂を製造する。(57) [Abstract] [Problem] It can be used for agricultural and horticultural materials, fishing materials, binders, etc., and is decomposed into carbon dioxide and water by hydrolysis and / or microorganisms in the soil even after disposal after use. To provide a method for easily producing a polyhydroxycarboxylic acid resin. A hydroxycarboxylic acid dimer (for example, L
-Lactide) or a mixture of a hydroxycarboxylic acid oligomer (for example, lactic acid oligomer) and a saccharide such as D-glucose or corn starch in a mixture of a polymerization catalyst (preferably a 1,3-substituted-1,1,3,3-tetraorganodistanno). Xan) is added, and the mixture is heated and stirred under reduced pressure, or is subjected to dehydration polymerization in an organic solvent to produce a polyhydroxycarboxylic acid resin.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は加水分解性及び生分
解性のポリヒドロキシカルボン酸樹脂の製造方法に関す
るものである。The present invention relates to a method for producing a hydrolyzable and biodegradable polyhydroxycarboxylic acid resin.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
種々の樹脂成形物が農業・園芸用資材（例えばポリ塩化
ビニルフィルム）及び漁業用資材（例えばポリエチレン
繊維の漁網）として用いられているが、これらの資材は
いずれは廃棄されるものである。したがって、廃棄され
ても公害源とならず、時間の経過とともに加水分解され
るか又は土中の微生物により生分解される樹脂が要望さ
れている。本発明は、このような農業・園芸用資材、漁
業用資材、粘結剤などに利用でき、使用後に廃棄されて
も加水分解及び／又は土中の微生物などにより二酸化炭
素と水に分解されるポリヒドロキシカルボン酸樹脂を容
易に製造する方法を提供することを目的とするものであ
る。2. Description of the Related Art
Various resin moldings are used as agricultural and horticultural materials (for example, polyvinyl chloride film) and fishing materials (for example, fishing nets made of polyethylene fibers), and these materials are eventually discarded. Therefore, there is a demand for a resin that does not become a pollution source even when discarded, and that is hydrolyzed over time or biodegraded by microorganisms in the soil. The present invention can be used for such agricultural and horticultural materials, fishery materials, binders, and the like, and is decomposed into carbon dioxide and water by hydrolysis and / or microorganisms in the soil even after disposal after use. It is an object of the present invention to provide a method for easily producing a polyhydroxycarboxylic acid resin.
【０００３】[0003]
【課題を解決するための手段】本発明者らは上記の目的
を達成するために鋭意検討の結果、ヒドロキシカルボン
酸二量体またはヒドロキシカルボン酸オリゴマーと糖類
との混合物中に重合触媒を添加し、脱水重合を行うこと
により加水分解性及び生分解性のポリヒドロキシカルボ
ン酸樹脂を製造することができることを見出し、本発明
を完成するに至った。Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, added a polymerization catalyst to a mixture of a hydroxycarboxylic acid dimer or a hydroxycarboxylic acid oligomer and a saccharide. It has been found that a hydrolyzable and biodegradable polyhydroxycarboxylic acid resin can be produced by performing dehydration polymerization, and the present invention has been completed.
【０００４】[0004]
【発明の実施の形態】本発明で使用するヒドロキシカル
ボン酸二量体またはヒドロキシカルボン酸オリゴマーと
しては、乳酸、グリコール酸、酒石酸、クエン酸、リン
ゴ酸、オキシ吉草酸、２−ヒドロキシステアリン酸、サ
リチル酸、ｏ−オキシケイ皮酸などの二量体またはオリ
ゴマー、あるいはこれらの混合物を挙げることができ
る。好ましいヒドロキシカルボン酸二量体は環状二量体
であり、特に好ましくはＬ−ラクチドである。また好ま
しいヒドロキシカルボン酸オリゴマーは乳酸オリゴマー
である。DETAILED DESCRIPTION OF THE INVENTION The hydroxycarboxylic acid dimer or hydroxycarboxylic acid oligomer used in the present invention includes lactic acid, glycolic acid, tartaric acid, citric acid, malic acid, oxyvaleric acid, 2-hydroxystearic acid, salicylic acid. And dimers or oligomers such as o-oxycinnamic acid, or a mixture thereof. Preferred hydroxycarboxylic acid dimers are cyclic dimers, particularly preferably L-lactide. A preferred hydroxycarboxylic acid oligomer is a lactic acid oligomer.
【０００５】本発明で使用する糖類としては、天然物の
ものが好ましく、Ｄ−グルコース、Ｄ−フルクトース、
Ｄ−マンノース、Ｄ−ガラクトースなどの単糖類、麦芽
糖、砂糖（ショ糖）などの少糖（オリゴ糖）類、澱粉、
特にコーンスターチ、サツマイモ澱粉、小麦澱粉などの
多糖類、あるいはこれらの混合物を挙げることができ
る。The saccharides used in the present invention are preferably natural products, such as D-glucose, D-fructose,
Monosaccharides such as D-mannose and D-galactose; oligosaccharides (oligosaccharides) such as maltose and sugar (sucrose); starch;
In particular, polysaccharides such as corn starch, sweet potato starch, wheat starch and the like, and mixtures thereof can be mentioned.
【０００６】本発明においてヒドロキシカルボン酸二量
体またはヒドロキシカルボン酸オリゴマーと糖類との重
合反応に用いられる重合触媒としては１，３−置換−
１，１，３，３−テトラオルガノジスタノキサンを挙げ
ることができる。ここで、スズ原子に結合するオルガノ
基はメチル基、エチル基、プロピル基、ブチル基、オク
チル基、アリル基、ベンジル基、フェニル基のいずれで
も良いが、溶解度やコストなどを考え合わせるとブチル
基が好ましい。また、１，３位の置換基はハロゲン、チ
オシアノ基、水酸基、アルコキシ基、カルボキシル基の
いずれでもよい。[0006] In the present invention, the polymerization catalyst used for the polymerization reaction of a hydroxycarboxylic acid dimer or a hydroxycarboxylic acid oligomer with a saccharide is 1,3-substituted-
1,1,3,3-tetraorganodistanoxane can be mentioned. Here, the organo group bonded to the tin atom may be any of a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, an allyl group, a benzyl group, and a phenyl group. Is preferred. The substituent at the 1,3-position may be any of a halogen, a thiocyano group, a hydroxyl group, an alkoxy group, and a carboxyl group.
【０００７】本発明で使用する重合触媒は、通常エステ
ル重合反応に使用されるいずれの触媒を使用してもよい
が、触媒活性が大きいこと、耐加水分解性が大きいこと
から１，３−置換−１，１，３，３−テトラオルがノジ
スタノキサンが好ましい。As the polymerization catalyst used in the present invention, any catalyst usually used for ester polymerization may be used. However, the 1,3-substituted catalyst has high catalytic activity and high hydrolysis resistance. -1,1,3,3-tetraol is preferably nodistanoxane.
【０００８】本発明で使用する有機溶媒としては、水よ
り沸点が高く、かつ水と相溶化しないものであれば、い
ずれでも良いが、天然物であり、かつ樹脂中に残存して
も環境及び人体に悪影響の少ないＤ−リモネンが好まし
い。なお、ヒドロキシカルボン酸の環状２量体と糖類を
出発原料として共重合体を合成する場合は、窒素気流下
で加熱攪拌するだけでよい。また、ヒドロキシカルボン
酸オリゴマーと糖類を出発原料として共重合体を合成す
る場合は、減圧下に加熱攪拌した脱水縮合反応を行う
か、または有機溶媒中で共沸脱水縮合反応を行うのがよ
い。また、ヒドロキシカルボン酸と糖類を出発原料とし
て共重合体を合成する場合は、減圧下に加熱攪拌した脱
水縮合反応を行うか、または、有機溶媒中で共沸脱水縮
合反応を行うのがよい。The organic solvent used in the present invention may be any organic solvent as long as it has a higher boiling point than water and is not compatible with water. D-limonene, which has little adverse effect on the human body, is preferred. When a copolymer is synthesized using a cyclic dimer of hydroxycarboxylic acid and a saccharide as starting materials, it is only necessary to heat and stir under a nitrogen stream. When a copolymer is synthesized using a hydroxycarboxylic acid oligomer and a saccharide as starting materials, it is preferable to carry out a dehydration-condensation reaction with heating and stirring under reduced pressure or to carry out an azeotropic dehydration-condensation reaction in an organic solvent. When a copolymer is synthesized using hydroxycarboxylic acid and a saccharide as starting materials, a dehydration-condensation reaction with heating and stirring under reduced pressure or an azeotropic dehydration-condensation reaction in an organic solvent is preferably performed.
【０００９】[0009]
【作用】上述した手段によって加水分解性及び生分解性
のポリヒドロキシカルボン酸樹脂をワンポットで容易か
つ効率よく製造することができる。これらの樹脂は廃棄
されても時間の経過とともに加水分解及び／又は土中の
微生物などにより二酸化炭素と水に分解される。According to the above-mentioned means, a hydrolyzable and biodegradable polyhydroxycarboxylic acid resin can be easily and efficiently produced in one pot. Even if these resins are discarded, they are hydrolyzed and / or decomposed into carbon dioxide and water by microorganisms in the soil with the passage of time.
【００１０】[0010]
（実施例１）Ｌ−ラクチド１ｍｏｌ（１４４ｇ）とコー
ンスターチ１４．４ｇと１，３−ジクロロー１、１、
３、３ーテトラブチルジスタノキサン０．２ｍｍｏｌ
（０．１ｇ）とを反応器に入れて窒素置換したのち、１
８０℃で２４時間撹伴した。得られた乳酸−澱粉共重合
体の重量平均分子量（Ｍｗ）は５７，０００であった。(Example 1) 1 mol (144 g) of L-lactide, 14.4 g of corn starch and 1,3-dichloro-1,1,
0.2 mmol of 3,3-tetrabutyldistannoxane
(0.1 g) in a reactor and the atmosphere is replaced with nitrogen.
Stirred at 80 ° C. for 24 hours. The weight average molecular weight (Mw) of the obtained lactic acid-starch copolymer was 57,000.
【００１１】なお、得られたポリヒドロキシカルボン酸
樹脂の分子量はＧＰＣを用いて測定した。溶媒はクロロ
ホルムを使用し、温度４０℃で流量は１．０ｍｌ／ｍｉ
ｎである。ＧＰＣ装置は日本ミリポアリミテッド（株）
製高圧ポンプ（高速液体クロマトグラフ用５１０型）
と、昭和電工（株）製示差屈折率検出器（Ｓｈｏｄｅｘ
ＲＩ−７１）およびカラムＧＰＣＫ８０６Ｍである。ま
た分子量はポリスチレンを標準試料とし、換算した値で
ある。The molecular weight of the obtained polyhydroxycarboxylic acid resin was measured by using GPC. The solvent used was chloroform, and the temperature was 40 ° C. and the flow rate was 1.0 ml / mi.
n. GPC equipment is manufactured by Japan Millipore Limited
High pressure pump (Model 510 for high-speed liquid chromatograph)
And Showa Denko's differential refractive index detector (Shodex)
RI-71) and column GPCK806M. The molecular weight is a value obtained by converting polystyrene as a standard sample.
【００１２】（実施例２）９０％Ｌ−乳酸１ｍｏｌ（１
００ｇ）とコーンスターチ１０ｇと１，３−ジクロロー
１、１、３、３ーテトラブチルジスタノキサン０．１ｍ
ｍｏｌ（５０ｍｇ）とを反応器に入れ、１７０℃で３時
間減圧下に加熱撹伴を行った。得られた乳酸オリゴマー
の重量平均分子量は１，２００であった。この中にコー
ンスターチ１０ｇを入れ、さらに１７０℃で１７時間加
熱撹伴を行った。得られた乳酸−澱粉共重合体の重量平
均分子量（Ｍｗ）は２８，０００であった。Example 2 1 mol of 90% L-lactic acid (1 mol
00g), 10 g of corn starch and 0.1 m of 1,3-dichloro-1,1,3,3-tetrabutyldistannoxane
mol (50 mg) was placed in a reactor, and heated and stirred at 170 ° C. for 3 hours under reduced pressure. The weight average molecular weight of the obtained lactic acid oligomer was 1,200. 10 g of corn starch was put therein, and the mixture was heated and stirred at 170 ° C. for 17 hours. The weight average molecular weight (Mw) of the obtained lactic acid-starch copolymer was 28,000.
【００１３】（加水分解促進試験による生分解性の評
価）一般に生分解性樹脂の微生物による分解は、まず加
水分解が起こり、樹脂の分子量の低下が起こったのち、
微生物による分解が起こることが知られている。したが
って生分解性樹脂については、加水分解性の評価をその
まま生分解性の評価方法の一つとして採用することがで
きる。そこで、ポリヒドロキシカルボン酸樹脂の易加水
分解性を評価するため、０．１Ｎ ＮａＯＨ水溶液中に
Ｍｗが１２，０００の乳酸ホモポリマーおよび乳酸−澱
粉共重合体の２ｍｍシートを浸漬して４日後の重量の減
少を測定した。最初の重量を１００とした場合、乳酸ホ
モポリマーは９１に減少したのに対し、乳酸−澱粉共重
合体は７５に減少した。このことから、本発明により得
られるポリヒドロキシカルボン酸樹脂はポリヒドロキシ
カルボン酸ホモポリマーと比べて生分解速度が大である
ことが判明した。(Evaluation of Biodegradability by Hydrolysis Acceleration Test) In general, biodegradation of a biodegradable resin by a microorganism first occurs after hydrolysis and a decrease in the molecular weight of the resin occurs.
It is known that degradation by microorganisms occurs. Therefore, for the biodegradable resin, the evaluation of the hydrolyzability can be directly employed as one of the methods for evaluating the biodegradability. Then, in order to evaluate the hydrolyzability of the polyhydroxycarboxylic acid resin, a 2 mm sheet of a lactic acid homopolymer and a lactic acid-starch copolymer having a Mw of 12,000 was immersed in a 0.1 N NaOH aqueous solution, and 4 days after the immersion. The weight loss was measured. When the initial weight was 100, the lactic acid homopolymer was reduced to 91, whereas the lactic acid-starch copolymer was reduced to 75. From this, it was found that the polyhydroxycarboxylic acid resin obtained by the present invention has a higher biodegradation rate than the polyhydroxycarboxylic acid homopolymer.
【００１４】[0014]
【発明の効果】以上説明したように本発明によれば、加
水分解性及び生分解性のポリヒドロキシカルボン酸樹脂
をワンポットで容易かつ効率よく製造することが出来、
得られた樹脂は粘結剤として、またその成形物は農業・
園芸用資材及び漁業用資材として使用することができ、
廃棄されても時間の経過とともに加水分解ないし土中の
微生物により二酸化炭素と水に分解されるので、公害源
とならない。As described above, according to the present invention, a hydrolyzable and biodegradable polyhydroxycarboxylic acid resin can be easily and efficiently produced in one pot.
The obtained resin is used as a binder,
It can be used as horticultural material and fishery material,
Even if discarded, it is not a source of pollution because it is hydrolyzed over time or decomposed into carbon dioxide and water by microorganisms in the soil.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 作田 信幸 広島県広島市西区三篠町２−２−８ 西川 ゴム工業株式会社内 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Nobuyuki Sakuta 2-2-8 Mishino-cho, Nishi-ku, Hiroshima-shi, Hiroshima Nishikawa Rubber Industries Co., Ltd.
Claims (6)
キシカルボン酸オリゴマーと糖類との混合物中に重合触
媒を添加し、脱水重合を行うことを特徴とするポリヒド
ロキシカルボン酸樹脂の製造方法。1. A method for producing a polyhydroxycarboxylic acid resin, comprising adding a polymerization catalyst to a mixture of a hydroxycarboxylic acid dimer or a hydroxycarboxylic acid oligomer and a saccharide and performing dehydration polymerization.
キシカルボン酸オリゴマーと糖類との混合物中に重合触
媒を添加し、減圧下に加熱攪拌するかまたは有機溶媒中
で脱水重合を行うことを特徴とするポリヒドロキシカル
ボン酸樹脂の製造方法。2. A method in which a polymerization catalyst is added to a mixture of a hydroxycarboxylic acid dimer or a hydroxycarboxylic acid oligomer and a saccharide, and the mixture is heated and stirred under reduced pressure or subjected to dehydration polymerization in an organic solvent. A method for producing a polyhydroxycarboxylic acid resin.
ドであり、ヒドロキシカルボン酸オリゴマーが乳酸オリ
ゴマーである請求項１または２記載のポリヒドロキシカ
ルボン酸樹脂の製造方法。3. The method for producing a polyhydroxycarboxylic acid resin according to claim 1, wherein the hydroxycarboxylic acid dimer is L-lactide and the hydroxycarboxylic acid oligomer is a lactic acid oligomer.
ス、Ｄ−マンノース、Ｄ−ガラクトースなどの単糖類、
麦芽糖、砂糖（ショ糖）などの少糖（オリゴ糖）類、コ
ーンスターチ、サツマイモ澱粉、小麦澱粉などの多糖
類、あるいはこれらの混合物である請求項１〜３の何れ
か１項記載のポリヒドロキシカルボン酸樹脂の製造方
法。4. The saccharides are monosaccharides such as D-glucose, D-fructose, D-mannose, D-galactose,
The polyhydroxycarboxylic acid according to any one of claims 1 to 3, which is a oligosaccharide (oligosaccharide) such as maltose or sugar (sucrose), a polysaccharide such as corn starch, sweet potato starch or wheat starch, or a mixture thereof. A method for producing an acid resin.
−テトラオルガノジスタノキサンである請求項１〜４の
いずれか１項記載のポリヒドロキシカルボン酸樹脂の製
造方法。5. A polymerization catalyst comprising 1,3-substituted-1,1,3,3
The method for producing a polyhydroxycarboxylic acid resin according to any one of claims 1 to 4, wherein the resin is a tetraorganodistanoxane.
カヒドロナフタレン）である請求項２〜５のいずれか１
項記載のポリヒドロキシカルボン酸樹脂の製造方法。6. The method according to claim 2, wherein the organic solvent is D-limonene or decalin (decahydronaphthalene).
The method for producing a polyhydroxycarboxylic acid resin according to the above item.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1150097A JPH10204157A (en) | 1997-01-24 | 1997-01-24 | Method for producing polyhydroxycarboxylic acid resin |
| DE19709854A DE19709854A1 (en) | 1996-03-13 | 1997-03-11 | Poly:hydroxy:carboxylic acid copolymer resin preparation |
| US08/816,139 US5844068A (en) | 1996-03-13 | 1997-03-12 | Process for the preparation of polyhydroxycarboxylic acid copolymer resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1150097A JPH10204157A (en) | 1997-01-24 | 1997-01-24 | Method for producing polyhydroxycarboxylic acid resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10204157A true JPH10204157A (en) | 1998-08-04 |
Family
ID=11779754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1150097A Pending JPH10204157A (en) | 1996-03-13 | 1997-01-24 | Method for producing polyhydroxycarboxylic acid resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10204157A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003012779A (en) * | 2001-06-29 | 2003-01-15 | Mitsui Chemicals Inc | Method for producing polyhydroxycarboxylic acid |
| JP2008031402A (en) * | 2006-06-29 | 2008-02-14 | Nagoya City | Castor hydrogenated oil-based reaction product, polylactic acid modifier, polylactic acid composition, and polylactic acid molded article |
| US7517937B2 (en) | 2003-05-08 | 2009-04-14 | Nishikawa Rubber Co., Ltd. | Biodegradable resin composition and biodegradable resin molded article |
| CN102863654A (en) * | 2012-10-11 | 2013-01-09 | 武汉华丽环保科技有限公司 | Starch and polylactic acid composite material and preparation method thereof |
-
1997
- 1997-01-24 JP JP1150097A patent/JPH10204157A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003012779A (en) * | 2001-06-29 | 2003-01-15 | Mitsui Chemicals Inc | Method for producing polyhydroxycarboxylic acid |
| US7517937B2 (en) | 2003-05-08 | 2009-04-14 | Nishikawa Rubber Co., Ltd. | Biodegradable resin composition and biodegradable resin molded article |
| JP2008031402A (en) * | 2006-06-29 | 2008-02-14 | Nagoya City | Castor hydrogenated oil-based reaction product, polylactic acid modifier, polylactic acid composition, and polylactic acid molded article |
| CN102863654A (en) * | 2012-10-11 | 2013-01-09 | 武汉华丽环保科技有限公司 | Starch and polylactic acid composite material and preparation method thereof |
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